SE407942B - HOT MELTING ADHESIVE COMPOSITION CONSISTING OF AN ACID ETHENEN COPY, A POLYAMIDE AND AN ADHESIVE - Google Patents

Description

in' n .s -... n _> ...'_..... ... am- .H-mq-.w-.a-a ... ms-L : 1313013-0 "2 tracts can easily drop to -40 ° C, and an answer cable or pipeline on the other hand in direct sunlight can reach surface temperatures of at least + 70 ° C.

A special use for hot melt adhesives is in connection with recoverable end caps and coats (ie those with elastic memory).

In recent years, increasing attention has been paid to the use of objects exhibiting the property of elastic memory in terms of the introduction of insulation for electrical wiring and cable ducts and similar nande. An object with this property is one that is deformed from an original, heat-stable dimensional shape to another, heat-unstable form. As long as this object is kept below a certain temperature, will it to maintain its unstable form but when heated over it temperature, called the recovery temperature, it will recover in the direction of its original form. A method of imparting material the property of elastic memory, and materials imparted therewith elastic memory, described in U.S. Pat. No. 3,086,242.

In general, measures are taken to establish an adhesive bond between the object with elastic memory and the substrate around which it is recovered, and in some cases the nature of the substrate has hindered in the way of making suitable dressings with hitherto available glue. For example, it has become common to use heat-shrinkable polyethylene for end caps for sealing polyethylene sheathed telecommunications cables, and much would be gained by extending this technology to lead mantle the cables for general use. Lead, however, is widely known as one substrate with poor adhesion, and the hitherto available adhesives have generally proved to be unsuitable, in that they often provide peeling strengths not significantly greater than about 5 N per linear cm at room temperature and even less at temperatures that are significantly below above or below room temperature. As already mentioned, however telephone cables can often be exposed to temperatures that are significantly above and below room temperature. According to current specifications for cable end sleeves require good peeling strength at + 70 ° C. Future specifications will undoubtedly require good peel strength both at -4000 and at + 70 ° C. In addition to exhibiting appropriate peeling strength above this temperature range, adhesive for end caps must soften at a temperature below that at which the end cap itself is lowered is broken but which is nevertheless much higher than the maximum operating temperature so that the end cap during operation is prevented from Å slide off the cable end. There has therefore been a need for an end-to-end glue with sufficient peeling strength both at high and low temperatures rations to allow applications including lead sheathed cables, .m '.a = 1 = - »« ... ~ ~ max-f. _ .e- .... | _.l. =.,. ... l 7313013-0 which glue nevertheless shows a low brittleness temperature and a softening temperature which makes it suitable for use in such applications cations. _ According to the invention, a hot melt adhesive composition is provided consisting of a combinable mixture of a) an acidic ethylene copolymer with an acid number ranging from about 3 to about 80; b) a polyamide with a amine number varying between about 70 and about 400, and c) a tackifier in a amount of 3 to 20 parts by weight per 100 parts by weight of a) and b) together.

The adhesive compositions of the invention may be prepared by mixing the three components at a temperature range of at least about 100 ° C and preferably about 150 ° C. Any suitable mixer, used for plasl composition, is suitable, tlex. one with steam jacket equipped with a differential rolling mill, a mixture with high shear forces dare or a sprayer. components a) and b) should preferably be present in weight ratios between a) and b) in the range from 40:60 to 60:40. The are preferably present in approximately equal amounts by weight. The amount of c) preferably constitutes about 5 - 15 parts by weight per 100 parts by weight of a) and b) together. As will be described in more detail below, amounts of these components which deviate significantly from those specified result in impaired adhesion.

The three components of the adhesive mixture must be compatible ( ra). The term compatible means in polymer chemistry that the mixture of, polymers have a single glass transition temperature, unlike those multiple glass transition temperatures characteristic of the walking polymers. All of the amides and ethylene polymers described herein are compatible with each other and with most common adhesives when they are mixed together in the manner described in the conditions indicated. The The compatibility of the three components can of course be determined by simply makes sure that the mixture has a single glass temperature. We have found that most common adhesives are compatible in the required quantities, and of course which any means which would prove incompatible could easily be by determining whether the mixture has a single glass conversion temperature. It should be emphasized that this type of compatibility between of different chemical types, ie amide and ethylene polymers, are country rare (see, e.g., J. Macromol. Sci., gl, p. 252 (1972) and U.S. Patent 3,484,403).

In the adhesive art, tackifiers are known additives in adhesive compositions. ___... u »..« _._ ~ .., ...-.._., .... .- »va -__» aa- ... n. 7313013-0 nings. The adhesive means known in the art comprise a large number natural and synthetic monomeric and polymeric substances, among which most have been found to be effective in the adhesive compositions of the invention.

Suitable tackifiers include the following: Hercules Hercules Alkali Diamond Éohm Ü Haas Argus Chemical Baker Castor Oil Hercules Hercules Hercules Hercules Pacific Vegetable Oil Bucket Ü Amend Neville Hercules Hercules' Hercules Hercules Pennsylvania Industrial Chemical Corporation Union Carbide Union Carbide Union Carbide Mohawk Ind.

Mohawk Ind.

Hercules Hercules Commercial name Åbalyn Abitol Chlorowax 70 Uibenzyl sebacate Drapex 3.2 15 Oil Flexalyn Hercoflex 150 Hercolyn Hydrolyn A Isano Oil Blystearat Nevillac 1o ° Petrex SS Polypale Ester 1 Polypale Ester IQ Staybelite Ester 10 Piccotex 75 ZKMÅ 0251 ZKMÅ 0252 'zKMA ozso R 97 MR 82 Resin 7310 a-Piccolyte 100 Chemical nature _ Methyl ester of rosin nysroabiecyl alcohol Chlorinated paraffin Esther _ _ Epoxy type plasticizer Polymerized (oxidized) castor oil Glycol ester of rosin n-Octyl n-decyl phthalate (mixture) Hydrogenated methyl ester of rosin Hydroabietyl alcohol ester Glyceride _Blystearat Hydroxyalkyl ester of rosin Alkyd of resinous terpenic acid Ethylene glycol ester of polymerized rosin Glycerol ester of polymerized rosin Glycerol ester of hydrogenated colophon name Vinyl-toluene copolymer Ketone plastic Ketone plastic Ketone plastic Aliphatic ketone plastic Aliphatic ketone plastic Dehydrated rosin Modified rosin Preferred tackifiers are low molecular weight, usually liquid tackifiers, in particular of the polyketone type, e.g. ketone plastics marketed by Union Carbide and Mbhawk Industries, Inc.

The absence of a tackifier or alternatively the use of one tackifiers in amounts outside the above proportions give a ._- =. ... s -........ man .. u »._. . .-. fi s saz ^ ngn = ._ a.¿_l fi => _ l fl. ~ sap uns ... 5 '7313013-0 inferior glue. The use of less than about 3 parts of adhesive in adhesive the composition may result in poor wetting of the substrate therefrom the following uneven adhesion with hard-bonded substrates, and if more than about 20 parts of tackifier are added, the adhesive usually shows insufficient peeling strength at any temperature with virtually any substrate.

Component a) is, as mentioned, an acidic ethylene copolymer, wherein this use the term copolymer includes ter and higher copolymers, for example. with two or more comonomers, but excludes graft polymers based on a polar science skeleton.

Component a) is preferably either a terpolymer of ethylene, a ethylenically unsaturated mono- or dicarboxylic acid and a vinyl ester of a aliphatic carboxylic acid with a straight or branched chain having 1 to 6 carbon atoms or, alternatively, a copolymer of ethylene and a C2 - C20 aliphatic ester of a monoethylenically unsaturated mono- or dicarboxylic acid. If so a mixture of such a terpolymer and such a copolymer may be desired be used.

In the case of the terpolymer, the weight percentage of those in each terpolymer molecule present units, derived from each of the three monomeric components, suitably being the following: Ethylene '60 - 95, preferably 70 - 85 Unsaturated mono- or dicarboxylic acid 1 - 10, preferably 2 - 5 Vinyl ester S-40, preferably 10-30 The presence of the units derived from the mono- or dicarboxylic acid in the indicated percentage will give enterpolymer with the desired the acid number. As stated below, terpolymers with acid numbers yield outside it specified area inferior glue. .

Vinyl esters of the aliphatic C1 - C6 carboxylic acids are known units of which most, e.g. vinyl acetate, vinyl propionate and vinyl butyrate, are commercially available. Any of these vinyl esters or any mixture thereof can be advantageously used.

In the case of the copolymer, the weight percentage of those in each copolymer molecule present units, which derive their origin from each of the monomeric components, suitably be as follows: ethylene 60-95, preferably 70-90, and, correspondingly, C aliphatic ester of monoethylenically unsaturated mono- or dicarboxylic acid 40 - 5, preferably 30 - 10. The desired acid number is achieved by to the polymerization batch add the appropriate amount of monomer ester in which the carboxylic acid moieties are not fully esterified.

Co- or terpolymer with acid numbers outside the specified range provides adhesives that are inferior by not providing the excellent benefits of ._ .k u. .fm-am .w _ 7313013-0 and 6- i the adhesive compositions of the invention. In contrast to conventional poly- amide glue, the glue according to the invention will not crack until temperatures below -4000 and in many cases not even below -70 ° C.

Conventional polyamide adhesives usually crack at low temperatures a good distance above -40 ° C. Conversely, conventional adhesives, which are based on copolymers and terpolymers of ethylene, not any useful peeling strength at room temperature and even less at + 70 ° C, while the adhesive according to the invention has good peeling strength at this temperature. _ It should also be emphasized that the mere combination of polyamide and ethylene co-or terpolymer lnm as such do not starves in a markedly superior adhesive composition. It's only when amides and ethylene co- and terpolymers with the specifics listed above the properties plus tackifiers are combined in the specified weight proportions as the superior properties appear. Even if we do not want to bind us at any particular explanation of this mechanism, it is assumed that \ it unusually low embrittlement temperature and high adhesive strength of the compositions according to the invention are due to the fact that the adhesive compositions are compatible mixtures. A mixture of polyamides or ethylene compounds , or terpolymers which do not have the properties listed above, give apparently not compatible mixtures, which thus do not show any of the excellent benefits. 7 Suitable ethylenically unsaturated mono- or dicarboxylic acids include those with from 3 to about SO 2 C atoms. Such acids may contain one or more double bonds and may be alicyclic or aliphatic.

Suitable acids include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, aconitic acid, itaconic acid, brassidic acid acid, α (1-cyclohexenyl) -butyric acid, 2-cyclopentene-1-acetic acid, 5-norbornene 2-carboxylic acid, 3-cyclohexene-1-carboxylic acid, endo-5-norbornene-2,3- dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, as well as citric acid and other acids which can be decomposed by the merization temperature to give unsaturated dicarboxylic acids situ, or mixtures of two or more of these acids.

The copolymers or terpolymers used according to the invention can easily prepared by copolymerizing a mixture of the the comonomers in the presence of a free radical initiator such as one per compound, e.g. lauroyl peroxide or t-butyl peracetate, or a azo-bis compound, e.g. azo-bis-isobutyronitrile, at elevated temperature, for example 90 - 2S0 ° C, and a pressure of 1000 - 1750 at., And separation of the polymer formed from the unpolymerized materials, e.g. through 1 7313013-0 that the latter evaporate. By varying the monomers used, the concentrations of the monomers and initiators in the reaction mixture one, and the reaction conditions, e.g. reaction time, pressure and temperature luckily, the desired degree of polymerization and acid number can be easily achieved.

The terpolymers can also be prepared by batch polymerization methods but thereby usually inhomogeneous polymers are formed. Continuous methods in which an appropriate mixture of the comonomers and the initiator fed continuously through one at the desired temperature and the desired the pressurized reaction zone, is definitely preferred because they provide practically homogeneous copolymers. The reaction zone and the volume flow of the reaction mixture fed thereby should be such that a appropriate residence time is ensured.

Ethylene terpolymer of the one used in the practice of the invention only the type and their preparation are described in U.S. Pat. publications 3,215,657 and 3,215,678 and in duPonts Elvax Product Information tion Bulletin PL16-1070. Although these patents and duPonts Formation specification describes the use of such terpolymerizates only or in combination with petroleum wax as a hot melt adhesive, it should It should be noted that these previously known adhesives are decidedly inferior to the adhesives according to the invention in terms of peel strength, in particular at temperatures above room temperature, and with respect to adhesion on hard-bound substrates such as lead.

The ethylenically ode acids useful in the practice of the invention the ester copolymers and their preparation are described in: Bonotto, S., Krevsky, B. H., SPE Journal, May 1962 and U.S. Pat. ten 2,953,541- Component b) will usually be a polyamide condensation copolymer of at least one diamine with at least one dicarboxylic acid, with dimer acid as the preferred predominant component of the dicarboxylic acid.

These condensation polymers are usually prepared by reacting a molar excess of the amine group-containing molecules with the carboxylic the acid group-containing molecules. The excess amine used must be large enough to give a polyamide with an amine number of variants. 7 those from about 70 to about 400. We have found that this amine number is required to give an adhesive with the above excellent properties.

Suitable diamines include primary diamines of the formula HZN-R-NH2 wherein R represents an aliphatic, cycloaliphatic or aromatic group, preferably having from 2 to about 40 carbon atoms. While R is preferably a hydrocarbon group, R may also optionally contain ether bridges as in those , 7s1zo1zëo g 8 . .u-.aa diamines prepared from diphenyl ether. If R ~ is an aliphatic group, can it be a saturated group with a straight or branched carbon chain. Representative for such diamines, the alkylenediamines having 2 to 20 carbon atoms (preferably desvis 2 - 6 C atoms) t.ei. ethylenediamine, 1,2-diaminopropane, 1,3- diaminobutane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and octadecamethylenediamine. In addition, you can use aliphatic diamines which are substituted by 1 to 3 lower alkyl groups or a higher alkyl group, e.g. 2,5-dimethyl-hexamethylenediamine, 2-methyl- 4-ethyl-hexamethylenediamine, 2-ethyl-4-methylhexamethylenediamine, a mixture of 2,4,4-trimethyl-hexamethylenediamine and 2,2,4-trimethyl-hexamethylenediamine or a mixture of 9-aminomethyl-stearylamine and 10-aminoethyl-stearyl- amin. Furthermore, aromatic diamines such as methaxylenediamine may be used, paraxylylene diamine and alicyclic diamines such as cyclohexylene diamine, 1,3-di-4-piperidyl-propane, bis (β-aminoethyl) -benzene, cyclohexane-bis- (methylamine), diamino-dicyclohexyl-methane, methylylene-dianiline, bis (amino- ethyl) -diphenyloxide and dimer fatty diamine. IN Dimerfettiamine, sometimes referred to as "dimerdiamine", Ndimerfettamine ", or "polymeric fatty acid diamine" means the diamines prepared by amination of dimeric fatty acids, to be described below; concerning these are referred to U.S. Pat. No. 3,010,782. As mentioned in this, these amines are prepared by reacting polymers fatty acids with ammonia to form the corresponding nitriles and hence hydrogenation of the nitriles to the corresponding amines. At distillation the dimeric fatty amine is obtained, which has essentially the same structure as a dimeric fatty acid except that the carboxyl groups have been replaced by -CHZNHZ groups. This diamine is also described in Research and Development Products Bulletin, CDS 2-63 by General Mills, Inc., June 1st 1963, such as "Dimer Diamine", illustrated by the formula HZN-D-NH 2, where D represents an approximately 36 C atoms containing hydrocarbon group of a dimer fatty acid.

Diamines, which are interrupted by oxygen atoms in the chain (also called ether diamines), and which are also suitable, can be represented by , the general formula: [nu ... nån -wgnm -.-'.-_- v -... fl "pi-un ..» a -... z- "J-.l-W ... _...

HZH- (CHQn-o- (R - o) x- (cH2) n-NH2 where n can be a number from 3 to 5, x can have a value of 0, 1, 2 or 3, and R represents an alkyl group having 1 to 12 carbon atoms, which group * may also be substituted with alkyl groups having 1 to 4 carbon atoms. Eczema pellets of ether diamines according to this general formula are: 1,7§diamino-4- oxoheptane, 1,11-diamino-oxoxundecane, 1,7-diamino-3,5-dioxoheptane, 1,10-diamino-4, oxy-undecane, 1,10-diamino-4, β-dioxa-s-methyldacane, 9 7313013-0 1,11-diamino-4,8-dioxoundecan, 1) 11-diamino-4,8-dioxo-5-ethylundecane, 1,12-diamino-4,9-dioxododecane, 1,13-diamino-4,10-dioxotridecane, 1,14- diamino-4,11-dioxotetradecane, 1,11-diamino-4,8-dioxo-5,6-dimethyl-7- propionylundecane, 1,14-diamino-4,7,10-trioxo-tetradecane, 1,13-diamino- 4,7,10-trioxo-5,8-dimethyltridecane, 1,20-diamino-4,17-dioxoeicosane and 1,16-diamino-4,7,10,13-tetraoxohexadecane. in Monoalkanolamines can also be used as starting material instead for or together with diamines. Suitable monoalkanolamines have preferably the general formula and NH -R-o fl 2 where R represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms.

Ethanolamine is preferred but other suitable compounds include propanol amine, butanolamine, 2-amino-3-hexanol, 2-amino-4-pentanol, S-amino-4- octanol, 3-amino-3-methyl-2-butanol and similar compounds. Such alkanolamines of course give polyesteramides._ The diamine can be used alone or can be mixtures of two or more diamines are used. The most preferred diamines are alkylene the diamines in which the alkylene group has 2-6 C atoms, and mixtures thereof with dimer fat-diamine.

As mentioned earlier, it consists of the polyamide component b) produced position using the dicarboxylic acid, preferably considering the dimer acid. By consideration is meant that about 60% of the carboxylic acid present the groups are present in the dimer acid component of a dicarboxylic acid mixture. It should be noted, however, that acceptable polyamines can produced using smaller amounts or t.o.m. no dimer- acid. Other suitable carboxylic acids should be listed below.

By dimer acid is meant a commercially available material which can be obtained by coupling unsaturated long chain fatty acids containing holding a carboxyl group, e.g. oleic or linoleic acid. The resulting the "dimer" is a mixture of many isomers, with varying degrees of unsaturation and ring formation, depending on the unsaturation of the starting materials degree. The exact structure of the isomers and the proportions of each isomer in the mixture varies with the combination method (which varies according to manufacturer), and of course also with the starting material or len. Trimers and products with higher degrees of polymerization are also available. so present to a lesser extent.

The structure of these dimeric acids has been subjected to comprehensive surveys. To give an indication of the background to this aspect of the invention, the following references have been included in a list, but it should be noted that the invention is not limited to those in f " ... 7313013--0 10 the structures indicated in the references., _ Based on the essay by_Pascke, R F, Peterson, L E and Wheeler, D H, Journal of the American Oil Chemists! Society, 41, 723 (1964); assumed that there are four possible structures for thermal dimers of 10-trans, 12- .trans-linoleic acid: _ v ' l “Wr- '^ ny! || ï-qn _ (cnß fi, .o å H 'u -H , \ (crlåh-c-c fl WH i ' (g fl a). _ '' ua. ' n- f crou (CH) e 2 H \ Äcr fi cu- (cnz,) ,, - cH_., H, -ñwlg k-coou (f-: Ha) 4 CH » '1313013-0 11 CIO -ou () a .o - I '5 _- HRS\ * (cn = cn- (en,), -IÉ-on .HH / . (one).

- Ha fr ...

IN NOT í.

EI-oxi ¿_ J Q Å CH; ) s * k _ / _ "(c fl _.,) ,, - c fl a 'WH -H-cu = cH- (cru) a ~~ |: -o + | (CHQ) Q - 'l ba, 7313013-0 1, It should be noted that the number of carbon atoms between the carbonyl carbon atoms varies between 18 and 21, ie the carbon chain contains 20 - 23 carbon more including the carbonyl carbon atoms. Furthermore, it should be noted that there is branches containing up to 9 carbon atoms excluding the ring carbon atoms.

In an essay by Cowan, J C, Journal of the American Oil Chemists' Society, 391, 723 (1962), the possible structures are generally discussed for similar dimers. In a publication by Emery Industries, Ino., Technical Bulletin 412B, "Abstracts of Dimer Acid Use-Patents and Journal Referenceså, January 1967, is given on p. 2 or 3 summaries of n a number of references, and in an essay by Paschke, R F, Peterson, L E, Harrison, S A and Wheeler, D H, Journal of the American Oil Chemists' Society, 41, 56 (1966), discusses the structures of the dehydrodimer from methyl oleate with di-tert-butyl peroxide. These references all refer in turn to other relevant literature. § The exact structure of these dimeric acids varies from manufacturers to manufacturers, but common to them is that they all contain laughs a mixture of isomers. At least some of the isomers, and in most cases all, contain some unsaturated carbon double bonds, and for increasing the oxidation stability of the one prepared therefrom amide, these double bonds are preferably removed by hydrogenation to form a saturated, or predominantly saturated, product. Despite that all dimeric acids can be converted to suitable starting materials for preparation of polyamides useful according to the invention, it has that the different manufacturing methods and the different starting materials used by the various manufacturers results in a number of ”Amides with slightly varying properties.

Other dicarboxylic acids are suitably used in place of, or added to, 'together with, dimeric acid for raising the softening point of those therefrom prepared polyamides. Suitable dicarboxylic acids include aliphatic, alicyclic or aromatic dicarboxylic acids or esters which may finished with the formulas: Rlooc-coonl and Rlooc-R-cooxl where R 1 represents hydrogen or an alkyl group, preferably with 1 - 8 C- atoms, and R is an aliphatic, alicyclic or aromatic hydrocarbon group, preferably with 1 to 20 carbon atoms (most preferred then being R represented by an alkylene group having 6 to 12 carbon atoms). Illustrative example on such acids are oxalic acid, malonic acid, adipic acid, sebacic acid, suberic acid acid, pimelic acid, azelaic acid, succinic acid, glutaric acid, isophthalic acid, terephthalic acid, the phthalic acids, benzene-acetic acid, p-phenylene-dipropionic acid, the naphthalene dicarboxylic acids and 1,4- or 1,3-cyclohexane dicarboxylic acid. . _ .. .... u.-..-. rhyme 13 7313013-0 The polyamides used in the practice of the invention should be treads have a meaelmolekylvikc ranging from about zboo to about 10 ooo ..

Illustrative examples of commercially available polyamides, which are suitable for incorporation into the adhesive compositions of the invention, are those which are described in U.S. Pat. Nos. 3,249,629 and f 3,449,273. The polyamides used according to the invention are prepared in conventional amidation methods which are not the subject of the invention.

This amidation is preferably carried out at a temperature varying between about 180 ° C and about 28,000 after simple mixing of the desired ones the amounts of the amine and the carboxylic acid. Reaction with the diamines results in in the formation of the desired polyamide plus the formation of RIOH (ie aqueous or alcohol). '? Additional components that can advantageously be added optionally the adhesive composition according to the invention comprises harder, active and active fillers, reinforcing agents, carriers and preservatives of known types. ' Although all the individual components of the adhesive composition according to the invention are known individually, it should be emphasized that the combination has never been suggested before. As mentioned earlier, the combination according to the invention is further uniquely superior in adhesive effect. activity compared to the individual components of the composition either individually or in any of the combinations known in the art hence. Such unexpected superiority should be demonstrated in more detail of the following examples, which illustrate the invention.

Example 1 Preparation of an approximate echiometric fat polgamide A 1-liter flask was equipped with a glass-shafted Teflon stirrer. coated blades, thermometer, nitrogen inlet pipe and Claisen essay. The piston was heated by means of a silicone oil bath on a hot plate with magnetic agitation scheme. The sampling system consisted of distillation an essay, a cooler, a publisher and a gas bubbler. Dimer acid (Empol 1010, neutralization equivalent 289.2, 348.2 g, 0.60 mol) and: hydrogenated distilled dimer diamine (neutralization equivalent 289, 92.9 g fi 0.17 mol) was added to the flask. Ethylenediamine (Matheson, Coleman and Bell, 99%, 30.5 ml, 27.1 g, 0.45 mol) was pipetted. Stirring on started immediately and the oil bath was heated. The temperature rose immediately-_ bare, and the contents of the flask thickened as salt formation took place room (no precipitate was formed). The flask contents were heated to 200 - 215 ° C during the course of about 1.5 hours, while a very slow stream of nitrogen gas was passed through the flask. As the temperature rose, in . ..._.......: ...... _. ._ _...

Mm ..... .. .__._ .. ~ -. M ..- ._ .. v ..... ww ... ...., ..-....-.-. . ß ..... »...... ..- ....... a; ¿= .... aa¿v -.« _.... s. ...... .. ....,. ~. _ ,,, __ ,, ___ _ _ 7313013-0 14 the mass became less viscous, and reaction water was released at 140 - 155 ° C.

The temperature was maintained at 205 - 215 ° C for about 3 hours while stirring rapidly. sat. After 3 hours at this temperature, the nitrogen inlet was shut off, the agitation was stopped, and the flask was carefully evacuated using a water jet pump. Heating at 210 - 215 ° C with applied vacuum continued for about 1 hour. The viscous, clear yellow melt was poured under one stream of nitrogen in a Teflon-lined vessel and cooled rapidly on dry ice.

The material is then cut into chips for analysis and composition.

Analysis: Internal viscosity (0.5% in CHCl 3; 30 ° C): 0.27; softening point (ring and sphere): 110 ° C; amintal (milliequivalents / kg sample by titration a chlorobenzene solution of the polyamide using HClO 4 in glacial acetic acid): 25.

Example 2 Preparation of an amino-rich fat polyemic The apparatus from the previous example was used. Dimer acid (Empol 1010, 348.2 g, 0.60 mol) and hydrogenated distilled dimer diamine (65.7 g, 0.11 mol) was added to the flask followed by ethylenediamine (36.3 ml, 0.54 mole). The heating and stirring were started as before and the temperature was ZOO - 21006 was held for about 4 hours. Heat and vacuum from the water jet pump The pen was applied without stirring for another 1 hour. The batch was worked up and cooled as before.

Analysis: Internal viscosity: 0.24; softening point: 101 ° C; amintal: 147.

Examples 3 - 5 A peeling test was performed as follows: 1. Polyethylene or lead sheathed telephone cable with approx. 1271mn length and 38f mm diameter was wiped with a solvent, e.g. methyl ethyl ketone or methylene chloride, to remove dirt and grease from the surface. 2. A glue film made of solution or molten with a width of approx. 64 mm, > 127 mm length and 0.64 mm thickness were rolled around the clean cable surface. 3. A pre-expanded, heat-recoverable, cross-linked polyethylene pipe was stepped over the adhesive layer and shrunk on the adhesive coated cable with a gas flame. This heating also caused the adhesive to melt and flow. The The normal heating time for this operation was about 2 minutes. 4. After cooling, cut the sheathed cable sample to five 25.4 mm wide segments, from which the copper wires were removed. The 25.4 mm wide segment was stepped over a cylindrical metal mandrel, which was fixed at the ends. The mandrel could rotate freely around its longitudinal axis. The mandrel is attached to a jig, which fits the jaws in one Instron test machine. 15 73130f | §f ~ 0 6. A longitudinal slit was taken across the 2554 mm dimension i the outer polyethylene tube down to the adhesive layer to form a flap, which was inserted into the upper clamping jaw of the test machine. ' 7. The adhesive joint that held the polyethylene pipe to the cable sheath was tested on peel strength. (This peeling test complies with ASTM D8176-69 except that the specimen is stripped from a mandrel fixture in instead of a T-peel configuration.) The test machine guide had set at a separation speed between the clamping jaws of 50.8 mm / min.

An encapsulation was available to enable testing of the adhesive binding strength at temperatures above or below room temperature.

The results are given in lb? per linear inch (pli) at break. A crime can either be a hesitant, ie occurs at the interface between the adhesive layer and either of the substrates; or cohesive, ie the adhesive force between the adhesive layer and the substrates exceed the cohesive force in either of the straten or in the glue layer itself, and crime does not occur to anyone interface without inside the mass of the adhesive or substrate. Glue, which is strong enough adhesion to cause cohesive crime, is of course highly desirable.

Example 3 The following test results were obtained using a) a polyethylene sheathed and b) a lead sheathed telephone cable. §Vskaln.- Tesg temp. haäåíâïthet Type of ::;: ?? 8Éï_ Sample (C) a) x b) x fracture Elm 4355 + Lä? <1? É ÉÉÉZÉÉÉ i <ï5 ° 1 °% lm * ° 251 +70 ~ o ~ o Adhesive H Polyamide acc. ex.1 -40 brittle - Adhesive -20 + 10% ZKMA 0251 +25 ca 10 2 Cohesive " +70 ~ 0 - Adhesive " Polyamide acc. ex.2; âg ïgrïgt I _; Éâgííåïï -äo ”F 1 °% ZKM ^ 0251 +70 ~ o - Adhesive fl A -40 brittle - Adhesive -20 B +25 fell apart - Adhesive " C +70 ~ 10 2 Cohesive " D -40 20 6 Cohesive <-50 E +70 S Cohesive " F +25 40 20 Cohesive fi _ " G +25 12 '2 Adhesive -30 H +25 10 3 Adhesive -20 _ ..._.......- __. .a -..- »......... .. ..., .m - .. aø-.h-.H _ .. 4 .., 7_313013-0 016 I +25 '46 f 16 Cohesive <-S0 J +25 p38 i 18 a xcohesivt '<-5o K +25 v25 - 14 Kohesivc <-5o p L + 7_o 8 '8 Icohesivt <-5o M +70> 1o 9 Køhesipvt '<-5o Nï +70 3 1 - Adhesive _30 0 +70> 10 7 Cohesive <-50 P fl o ~ o - 'Adhesivc -3o Q i 170 ~ o - Adhesive -zo R _ Wo 3 3 Cohesive <-5o S% 7O 4 2 Cohesive -45 T +70 <1 <1 Cohesive -45 U +70 <1 <1 Cohesive <-SO f: i a) indicates peeling strength on polyethylene sheathed cable; b) indicates peel strength on lead sheathed cable.

The ethylene terpolymer used in Samples A - U in Example 3 was duPont Elvax 4355. This material is a terpolymer of ethylene (74%), vinyl acetate (25%) and methacrylic acid (<1%) (weight percent), and has an acid number of about 6. All samples A - P contained equal amounts of Elvax and polyamide. Samples A - U contained 10 parts by weight of ZKMA 0251 adhesive per 100 parts by weight Eleven; + polyamide. All samples were prepared by mixing of the constituents in a composite extruder at 15000. All samples A - U had softening points, determined by ring and sphere, in the range 90 - 160 ° C. When the samples were tested on glass transition temperature, samples D - F, 1, J, K; L, M, O, R, S, T and U one single glass transition temperature, while samples A - C, G, H, N, P and Q showed two clear peaks.

The test ingredients were as follows A - C: Polyamide according to Example 1 D - F: Polyamide according to Example 2 G: Versalon 1165 (General Mills polyamide), amintal = ZS (amide av dimer acid and ethylenediamine) J H: Coramide 230 (Cooper Polymer), amintal = 53 In: Versalon 1140 (General Mills), amide of dimeric acid, sebacic acid, ethylenediamine and dipiperidylpropane, amintal = 150 J: Versalon 1300 (General Mills), amide of dimeric acid, ethylenediamine and dimer diamine, amintal = 180 K: Polyamide prepared according to Example 2 but containing ethylene amine in sufficient quantity to give an amine number of 619 L “.«> ~ ._. ».. 17 7313013-0 " V < L: Polyamide prepared according to Example 1 from an 80:20 mol% mixture of Empol 1010 (dimer acid) and phthalic acid and butanol in sufficient to give the polyamide an amine number of 110.

M: Polyamide prepared according to Example 1 from Empol 1014 (mixture of dimer and trimer acid) and excess decamethylenediamine (amine- number = 150).

N: Same as M but limited excess of diamine (amintal = 50).

O: Polyamide prepared according to Example 1 using a 50:50 1 mole percent mixture of Empol 1010 dimer acid and sebainic acid and a 50:50 mole percent mixture of trimethylene-piperidine and dimer diamine, amintal = 130. J P; Same as Ö but limited excess of amine, amine number = 44.

Q: Elvax 4355 (60% by weight) plus polyamide according to Example 1 (40% by weight).

R: Elvax 4355 (60% by weight) plus polyamide according to Example 2 (40% by weight).

A: Elvax 4355 (40% by weight) plus polyamide according to Example 2 (60% by weight).

T: Elvax 4355 (25% by weight) plus polyamide according to Example 2 (75% by weight).

U: Elvax 4355 (75% by weight) plus polyamide according to Example 2 (25% by weight).

Example Q A number of ethylene copolymers and copolymers were tested for adhesion. strength both alone and together with polyamide. All samples in- contained ZKMA 0251 (10 parts by weight of 100 parts by weight of ethylene polymer or mixed ethylene polymer and polyamide). In all samples containing polyamide plus ethylene polymer, the weight ratio of ethylene polymer / polyamide was 50:50. IN In all cases, the polyamide used was substantially identical to it prepared according to Example 2.

The samples were as follows. Samples A - E were the duPont Elvax terpolymer namely terpolymers of ethylene, methacrylic acid and vinyl acetate with the following approximate compositions. * A: Elvax 4260: vinyl acetate 28%, methacrylic acid <10%, ethylene 71%; acid number = 6 B: Elvax 3689.3: vinyl acetate 12%, methacrylic acid 4%, ethylene 84%; acid number = 30 C: Elvax 3633.6: vinyl acetate 24%, methacrylic acid 4%, ethylene 72%; acid number = 30 D: Elvax 4355: vinyl acetate 25%, methacrylic acid 1%, ethylene 74%; acid- number = 6 . .. ...__ ....._._. o ....... o ... ....... ». ..._: ....-... ..-. ».., ...». _... _ .. _-. vz1'zo1z-o o: E: - Elvax 3633.3: vinyl acetate 28%, methacrylic acid 4%, ethylene 68%; acid number = -20 I ' Samples F - H are copolymers of ethylene and acrylic acid containing 6%, 15% resp. 20% acrylic acid. Sample I is a modified copolymer of ethylene and ethyl acrylate (18%) where a portion of the ethyl acrylate has been saponified and then acidified to provide the necessary acid groups.

The polymers of samples F - H were effective in combination with polyamide, thus showing that copolymers of ethylene with unsaturated acid without any ester components present are also effective. Sample I demonstrates another method of achieving the desired acid number. One* ethylenically unsaturated ester copolymer can thus be modified by partial saponification and then acidified to achieve the desired acidity. the number. The commercial name and acid number of these samples are jande: F: Union Carbide EAA 9060, acid number 45 G: Union Carbide EAA 9320, acid number 115 H: Union Carbide EAA 9300, acid number = 150 In: Union Carbide DPD 9169, acid number 35 J - L: Elvax 4260 plus polyamide M - 0: Elvax 3689.3 plus polyamide P: Elvax 3633.6 plus polyamide Q: 'Elvax 3633.3 plus polyamide R: DPD 9169 (modify / o) plus polyamide A: DPD 9169 (modified to acid number = 2) plus polyamide T: DPD 9169 (modified to acid number = 7) Plus polyamide U: DPD 9169 (modified to oxygen number 35) plus polyamide V: Experimental terpolymer of ethylene (65%), vinyl acetate (20%), methacrylic acid (15%), acid number = 100, plus polyamide W: Experimental terpolymer of ethylene (75 +%), vinyl acetate (24%) and methacrylic acid (0.2S%), acid number = 2 X: Experimental terpolymer containing 75% by weight of ethylene, 20% by weight of vinyl propionate and 5% by weight of tetrahydro- Il Il phthalic acid, acid number = 15, plus polyamide Y! Experimental copolymer containing 80% by weight of ethylene OH 20% by weight mixture of mono- and diethyl maleate with added sufficient monoethyl maleate present to give an acid number of 10 Z: Union Carbide EAA 9060 plus polyamide AA: Union Carbide EAA 9320 plus polyamide BB: 'Union Carbide EAA 9300 plus polyamide .... ~ ..-. . ...--, - - .. ß m. H ..-...-. ¿..... _ .. w% 7313013-0 Peel off. »' strength "Brittleness Test $ ___; ___ Lgl¿l ___ ;; low temperature Pm fsgg- a * b) <° c> A +25 '1o 3 Adhesivc <_50 B +25 12 2 Adhesive <~ 50 C +25 15 3 Adhesive <-SO n ï +25 _11 2 Adhesive <-5ø F. +25 '1 1 2 Adhesivc <-5o F +25 7 2 Adhesive <-50 G +25 5 2 Adhesive <-50 H +25 in 5 1 Adhesive <-5o I +25 _ 20 4 Adhesive <-50 J -40 35 10 Cohesive <-50 K +25 ~ 5O 20 Cohesive '<-SO L +70 '> 10> IO Kohesivb <-50 M -40 30 8 Cohesive <-50 N _ +25 45 18 Cohesive <-SO 0 +70> 10 9 Cohesive _ <-50 P -4Û 25 7 KOhGSiVb <-50 Q -40 27 9 Cohesive - <- 50 R -40 S 2 Adhesive <-50 S -40 7 3 Adhesive _ M-30 T -40 15 6 Cohesive <-50 U -40 32 9 Cohesive <-50 V +25 19 4 Adhesive <-50 W +25 IS 2 Adhesive -30 x +25 41 16 Cohesive <-So Y +25 37 14 Cohesive <-50 Z +25 SS 13 Cohesive (-50 AA +70 1 Adhesive <-SO BB -40 S 1, AdhesiVt <-S0 a ... ...... _, ..... x a) Peeling strength of polyethylene sheathed cable, b) Peeling holding phase with lead sheathed cable ,. . a. .we ......._...... n., .._->. .., ...... lßsal. _ _... m ...- - _ .. va-Åw -... mkl-a. ._ 7313013-0 20 The melt index of a polymer (M.I.) is known to be related to its molecular weight; the lower the melt index, the higher the molecular weight._Melt index of our polymers was determined according to the provisional test method den ASTM D1238-70, Condition E (ASTM Standards, 1972, Part 27, p. Å24 - 434). The value indicates the weight in grams extruded through a mouthpiece piece 2.1 mm (0.0825 inch) in diameter and 8.0 mm (0.315 inch) in length for 10 minutes at 190 ° C under a pressure of 2160 grams. The values of the melt index of the polymers according to the invention can vary from 0.5 to 200 and is usually from about S to 25 for an easy flow material must be obtained. Particularly preferred adhesive compositions are is held when the polyamide has an amine number varying, from about 100 to 300 and the ethylene copolymer or terpolymer has an acid number ranging from about 5 to 40.

Example 5 Several tackifiers were also tried. In all cases shown the adhesive composition a single glass transition temperature. All compositions- S0 contained parts by weight Versalon 1300, 50 parts Elvax 4260 and 10 parts allows adhesive. All tests were performed at + 70 ° C. In all low-brittle temperature below -4006.

Peeling strength _ --Lnlàl-- ~ Typ av Adhesives of *. 10) * crime ZKMA O25l I> 10 D40 Cohesive Alpha Piccolyte 100 9 8 Cohesive Polypale No. 1 ~ 10 8 Cohesive Nothing 7 5 Cohesive Arochlor 1260 8 6 Cohesive Chlorowax 70. 10 ~ 6 Cohesive Flexol 3GO 9 6 Cohesive Santicizer 8 8 6 Cohesive Pentalyn C 9 7 Cohesive Nevillac 100 9 8 Cohesive Drapex 3.2 8 6 Cohesive 5 ua) Peeling strength of polyethylene sheathed cable, b) peeling durability of lead sheathed cable Most of the above-mentioned tackifiers have been mentioned earlier in the description. The following are, however, although not described previously, likewise, as those immediately reported above the results show. 21? 7313013-0 Chemical nature Supplier Trade name Monsanto Arochlor 1260 1 Chlorinated biphenyl Union Carbide Flexol 3G0 Triethylene glycol-di (2-ethyl- kapronat) Monsanto Santicizer 8 N-ethyl mixed o- and p-toluene- sulfonamides' Argus Chemical Drapex 3.2 Epoxy type plasticizer In summary, it appears that the adhesive compositions according to the invention none, beyond its superior peeling strength at high and low temperature, which is of great advantage in cable insulation, especially when this applies to polyethylene and lead sheathed cables, and their low brittleness at low temperature, shows a softening point, measured according to the method with ring and ball, which is in the range from about 90 ° C - 160 ° C and thus has particularly suitable flowability for use with heat recoverable end caps and sleeves of polyethylene.

Claims (17)

. .f- »u -... a -. n na-l ~ aa_ .na .__ -_._._ ß -_. a. . n-'va: .gm-.af-. fl. <._., - .. ¿..... a._ ._ __ .. .l i .. .. .na-.w-. fl el -... L »__-. '<..- \ _ ~ _..- .. l .. l. xa.? 3'f3013'0 Kn ad -k ä nnetecknad 22 PÅTENTKRAV A hot melt adhesive composition, characterized in that it consists of a combinable mixture of a) an acidic ethylene copolymer having an acid number ranging from about 3 to about 80; b) a polyamide having an amine number ranging from about 70 to about 400; and c) a tackifier in an amount of 3 to 20 parts by weight per 100 parts by weight of a) and b) together. š ' 2. Hot melt adhesive composition according to box 1, characterized in that components a) and b) are present in the weight channel between a) and b) in the range from 40260 to 60:40. Hot melt adhesive composition according to claim 1 or 2, characterized in that the tackifier is present in an amount ranging from about 5 to about 15 parts by weight per 100 parts by weight of a) and b) together. Hot-melt adhesive composition according to any one of claims 1 to 3, wherein the adhesive is a ketone plastic. Hot melt adhesive composition according to any one of claims 1 to 4, characterized in that component a) is a terpolymer of ethylene, an ethylenically unsaturated mono- or dicarboxylic acid and a vinyl ester of an aliphatic carboxylic acid having 1- 6 C atoms in the aliphatic group. Hot-melt adhesive composition according to claim 5, characterized in that the vinyl ester is vinyl acetate. Hot melt adhesive composition according to claim 5 or 6, characterized in that the unsaturated acid is acrylic acid, methacrylic acid or a mixture thereof. Hot melt adhesive composition according to any one of claims 5 to 7, characterized by the units present in the polymer, which are derived from the three mono-§ more precursors of the terpolymer are: ethylene, 60 - 95; ethylenically unsaturated mono- or dicarboxylic acid, 1-10; and vinyl ester of C1 - C6 carboxylic acid, 5 - 40. 9. Hot melt adhesive composition according to claim 8, characterized in that the weight percentages are ethylene, 70-85; omlttad acid, 2 -_5; and vinyl ester, 10 - 30. Hot-melt adhesive composition according to any one of claims 1 to 4, wherein the weight percentage of those in ter-. ... w ........ ~ ..... ......._..._ ...___-_ i ... ._ '\ 23 7313013-0 k ä characterized in that component a) is a copolymer of ethylene and a C2 - C20 aliphatic ester of a monoethylenically unsaturated mono- or dicarboxylic acid, in which the mono- or dicarboxylic acid component is incompletely esterified. ll. Hot melt adhesive composition according to claim 10, characterized in that the weight percent content of the units present in the copolymer derived from the monomeric precursors of the copolymer are: ethylene, 60 - 95, and C2 - C20 aliphatic ester of monoethylenically unsaturated mono or dicarboxylic acid, S - 40. Hot-melt adhesive composition according to claim 11, characterized in that the weight percentages are: ethylene, 70-90, and aliphatic ester, 10 -50. ' Hot-melt adhesive composition according to any one of claims 10 to 12, characterized in that the unsaturated ear is acrylic acid, methacrylic acid, maleic acid or fumaric acid. Hot melt adhesive composition according to any one of claims 1 to 13, characterized in that component b) is a condensation polymer of at least one diamine or at least one monoalkano / amine with at least one dibasic acid. Hot-melt adhesive composition according to claim 14, characterized in that the two-base component consists of at least 60% by weight of dimer acid. * l6. Hot melt adhesive composition according to claim 14 or 15, characterized in that the diamine has the formula HZNRNHZ, where R represents an aliphatic, aliocyclic or aromatic group having 2 to 40 carbon atoms. 17. A hot melt adhesive composition according to claim 16, characterized in that the diamine is an alkylenediamine having 2 to 6 carbon atoms, dimeric fatty diamine or a mixture thereof. PROMISED PUBLICATIONS: Sweden patent application 4,897/72 US 3,377,305 (260-27)